KR970006753B1 - Polyetherester block copolymer resin composition - Google Patents

Abstract

Title copolymer resin having an improved melting strength and viscosity, was prepared by adding a flexible styrene material in polyetherester block copolymer resin. The composition comprises 10:90- 90:10 weight ratio of polyetherester block copolymer resin and a flexible styrene material such as styrene-butadiene rubber, thermoplastic styrene-butadiene elastomer. Thus, polyetherester block copolymer resin(KOPEL, KP3340), flexible styrene material(CARIFLEX 1102) and 0.3 wt.% of tetrakis[methylene-3(3,5-di-tert-butyl-4-hydroxy phenyl)propionate methane of the total resin amount were reacted at 220 deg.C, and dried at 100 deg.C for 6 hours to give the title resin composition.

Description

Polyetherester Block Copolymer Resin Composition

The present invention relates to a polyether ester block copolymer resin composition, and more particularly, to a polyether ester block copolymer resin composition having improved melt strength and viscosity by mixing a styrene-based flexible material with a polyether ester block copolymer resin. will be.

In general, polyether ester block copolymer resins have properties of remarkably excellent physical properties because constituents of hard segments are crystalline polyether components, which are high-strength engineering plastics, compared to styrene, olefin, and urethane-based elastic materials. have.

For example, tensile strength, yield strength, flexural modulus, etc. are superior to various elastic materials based on conventional general-purpose resins, and in particular, due to the excellent properties of hard segments, stability to heat and light and stability to various compounds This is an excellent elastic material that is characterized by an extremely high and rapidly increasing use and application in the market despite the relatively high price. In addition, since the soft-segment component copolymerized to give the rubber properties is a polyether component having a glass transition temperature of -100 ° C, the softness at the low temperature is very low, and thus the flexibility and rigidity at high and low temperatures are balanced. It is also a good material that provides a wide range of operating temperatures.

However, the polyether ester block copolymer resin having such characteristics has a low melt viscosity due to the flexibility of the ether bond and the sensitivity to heat because the soft segment used is a polyether component. In order to solve these drawbacks, many efforts have been made to improve the production or use of polyether ester block copolymer resins.

For example, US Pat. No. 4,000,000 discloses melting by forming a crosslink by adding a small amount of a component having at least three hydroxy or carboxyl groups capable of forming polyester in the process of preparing a linear polyether ester block copolymer resin. In order to improve the strength, the content of the cross-linking agent added in the process of preparing the resin is accompanied by a lot of restrictions in the subsequent process, so that the input amount is extremely small and the melt strength is improved in the range that does not inhibit the thermoplasticity of the polyether ester block copolymer resin. The effect had a minor disadvantage.

In order to solve this problem, it was concluded that the method of improving the melt strength of the resin in the post-process rather than during the polymerization process was the most efficient, and the present inventors were partially compatible with the polyether ester block copolymer resin component while experimenting with various compositions. Although it is excellent in flexibility and mixed with the polyether ester block copolymer resin, it is concluded that the component that minimizes the deterioration of various physical properties and flexibility is a styrene-based flexible material and completed the present invention.

Accordingly, an object of the present invention is to provide a polyether ester block copolymer resin composition having excellent physical properties and particularly improved melt strength and viscosity.

Hereinafter, the present invention will be described in detail.

The present invention is a polyether ester block copolymer resin composition comprising a polyetherester block copolymer resin and a styrene-based flexible material in a weight ratio of 10:90 to 90:10.

Hereinafter, the present invention will be described in more detail.

In general, the polyether ester block copolymer consists of a block copolymer of a hard segment represented by the following structural formula (I) and a soft segment represented by the following structural formula (II).

In the above formula, R is an aliphatic dicarboxylic acid such as terephthalic acid or its lower alkyl ester alone, or aromatic dicarboxylic acid such as isophthalic acid, old phthalic acid, naphthalenedicarboxylic acid, or adipic acid, sebacic acid, dimer acid, or the like. Mixtures with aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid may be used. As D, an aliphatic glycol component having 2 to 8 carbon atoms is used, and mainly 1,4-butanediol is used, and ethylene glycol, 1, 2- or 1,3-propylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol may be mixed, and G is a polyalkyl having a molecular weight of 300 to 6,000. The lenoxide glycol component is used, and poly (tetramethylene oxide) glycol is mainly used, and polyethylene glycol or polypropylene glycol is used alone or in a mixture. It may be used to.

In addition to the components constituting the polyether ester block copolymer in order to improve the melt viscosity of the polyether ester block copolymer as described above may be prepared by adding a component capable of inducing chemical crosslinking in the polymerization process, such a crosslinking agent component Crosslinking agents that have three or more primary or secondary amine groups, hydroxy groups or carboxyl groups and can form a three-dimensional network structure in the process of producing a polyether ester block copolymer resin can be used alone or in the form of a mixture. In addition, 0.1 to 1.0 mol% of a component having three or more functional groups capable of reacting with the polyester-forming component may be added to the R component of the structural formula to prepare a polyetherester block copolymer having excellent melt viscosity first.

At this time, the component that can be used as a crosslinking agent is trimellitic acid or its anhydride, pyromellitic acid or its anhydride, hexaglycerol, diethanolamine, triethanolamine, hexamethylenebis (aminoacetic acid), tricin, D- or DL-serine, DL-threonine hemihydrate, DL-aspartic acid, DL-2-methylglutamic acid, 2-aminoadipic acid, tris (hydroxymethyl) aminomethane, pentaerythritol, glyceric acid, gloconic acid, gluheptonic acid, etc. Can be used.

At this time, if the crosslinking agent component is used less than 0.1 mol% with respect to the acid component R, it is not expected to improve the desired melt viscosity, and when used in excess of 1.0 mol%, as mentioned above, condensation polymerization by excessively increasing the melt viscosity It is difficult to remove the low-molecular weight material generated during the process due to the difficulty in generating or discharging bubbles during the polymerization degree rise and discharge, and in some cases impossible to discharge.

In addition, the styrene-based flexible material that can be used in the present invention is styrene-butadiene rubber or thermoplastic styrene-butadiene elastic material, and in recent years, various similar materials developed to improve various problems of the styrene-based flexible material. The styrene-based flexible material has a lower limit of flexibility than the polyether ester block copolymer resin, which is excellent in flexibility and has a benzene structure in the structure. It has the characteristic that it is excellent in compatibility with an ester block copolymer resin component.

The polyetherester block copolymer mixed resin composition prepared according to the present invention can exhibit more flexibility than the polyetherester block copolymer resin alone, and the specific gravity is low due to the low specific gravity of the styrene-based flexible material. In addition, it has the characteristics of improving the melt strength and viscosity by reducing the sensitivity to heat, so it shows excellent molding characteristics during extrusion processing and blow molding, so it can be usefully used for wire coating or various extruded products.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.

Example 1

The resin component is composed of the composition shown in Table 1 below using KOPEL KP3340 manufactured by Kolon Co., Ltd. as a polyetherester block copolymer resin, and CARIFLEX 1102 manufactured by SHELL as a styrene-based flexible material. Tetrakis [methylene-3 (3,5-di-tert-butyl-4-hydroxy-phenyl) propionate] methane (trade name Iganox-1010 manufactured by Ciba-Geigy Co., Ltd.) was used as a heat stabilizer. Using 0.3% by weight of the total amount, the pellet-formed product manufactured by mixing with a hot melt kneading extruder in the form of a twin screw heated to 220 ° C. was dried in a dehumidifying hot air dryer at 100 ° C. for 6 hours to remove moisture. A polyether ester block copolymer mixed resin composition was prepared.

The polyether ester block copolymer mixed resin composition thus prepared was prepared in the injection molding machine having a transverse force of 150 tons at a cylinder temperature of 210 ° C., and the physical properties thereof were measured and shown in Table 1 below.

EXAMPLES 2-8, COMPARATIVE EXAMPLES 1-3

The composition and conditions in Example 1 were changed as shown in Table 1 below, and various physical properties were measured and shown in Table 1 below.

* TPEE: Polyetherester block copolymer resin (type / content)

B: KP3363 (polyether ester block copolymer of Kolon Co., Ltd. hardness 63D)

C: KP3355 (polyether ester block copolymer of hardness 55D of Kolon Corporation)

D: KP3340 (polyether ester block copolymer of hardness 40D of Kolon Corporation)

* SBC: Styrene Flexible Material

A: CARIFLEX TR 1101 (Styrene-based flexible material of Shell company, styrene content 31% by weight)

B: CARIFLEX TR 1102 (Styrene-based flexible material of shell company, styrene content 29% by weight)

C: CARIFLEX TR 1113S (Styrene-based flexible material of shell company, styrene content 35% by weight)

* T1: Processing temperature of hot melt mixing extruder in the form of twin screw

* T2: Injection Molding Temperature

* Hardness: Duro-Meta Hardness according to ASTM D-2240 (D TYPE)

* Tensile strength: Tensile strength according to ASTM D-638

* Elongation: Tensile elongation according to ASTM D-638

* Impact strength: room temperature Izod notch impact strength according to ASTM D-256

* Flexural modulus: Flexural modulus in accordance with ASTM D-790

* Melt index: Flowability / Measured temperature under 2160g load according to ASTM D-1238

Claims (2)

A polyetherester block copolymer resin composition comprising a polyetherester block copolymer resin and a styrene-based flexible material in a weight ratio of 10:90 to 90:10. The polyetherester block copolymer resin composition according to claim 1, wherein the styrene-based flexible material is a styrene-butadiene rubber or a thermoplastic styrene-butadiene elastomer.